WO2007081105A1 - Process for polymerization or copolymerization of ethylene - Google Patents
Process for polymerization or copolymerization of ethylene Download PDFInfo
- Publication number
- WO2007081105A1 WO2007081105A1 PCT/KR2006/005848 KR2006005848W WO2007081105A1 WO 2007081105 A1 WO2007081105 A1 WO 2007081105A1 KR 2006005848 W KR2006005848 W KR 2006005848W WO 2007081105 A1 WO2007081105 A1 WO 2007081105A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- compound
- group
- titanium
- catalyst
- polymerization
- Prior art date
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000008569 process Effects 0.000 title claims abstract description 34
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000005977 Ethylene Substances 0.000 title claims abstract description 26
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 76
- 239000010936 titanium Substances 0.000 claims abstract description 54
- -1 ester compound Chemical class 0.000 claims abstract description 49
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 39
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 26
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 24
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 13
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 10
- 229930195734 saturated hydrocarbon Natural products 0.000 claims abstract description 10
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 7
- 230000000737 periodic effect Effects 0.000 claims abstract description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 3
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 2
- FCBJLBCGHCTPAQ-UHFFFAOYSA-N 1-fluorobutane Chemical compound CCCCF FCBJLBCGHCTPAQ-UHFFFAOYSA-N 0.000 claims description 2
- ANGGPYSFTXVERY-UHFFFAOYSA-N 2-iodo-2-methylpropane Chemical compound CC(C)(C)I ANGGPYSFTXVERY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 2
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 claims description 2
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 2
- 229910003074 TiCl4 Inorganic materials 0.000 claims 1
- 229910010386 TiI4 Inorganic materials 0.000 claims 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 229920000642 polymer Polymers 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 15
- 229910052749 magnesium Inorganic materials 0.000 description 14
- 239000011777 magnesium Substances 0.000 description 14
- 239000000460 chlorine Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 10
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000037048 polymerization activity Effects 0.000 description 4
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000004292 cyclic ethers Chemical class 0.000 description 3
- 238000012685 gas phase polymerization Methods 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000005049 silicon tetrachloride Substances 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- DNUPYEDSAQDUSO-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl benzoate Chemical compound OCCOCCOC(=O)C1=CC=CC=C1 DNUPYEDSAQDUSO-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- LSWRBVSEWBWTDR-UHFFFAOYSA-N 2-hydroxyethyl benzoate Chemical compound OCCOC(=O)C1=CC=CC=C1 LSWRBVSEWBWTDR-UHFFFAOYSA-N 0.000 description 2
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 2
- LVYLCBNXHHHPSB-UHFFFAOYSA-N 2-hydroxyethyl salicylate Chemical compound OCCOC(=O)C1=CC=CC=C1O LVYLCBNXHHHPSB-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- OMSUIQOIVADKIM-UHFFFAOYSA-N ethyl 3-hydroxybutyrate Chemical compound CCOC(=O)CC(C)O OMSUIQOIVADKIM-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- 229940095095 2-hydroxyethyl acrylate Drugs 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- RFONJRMUUALMBA-UHFFFAOYSA-N 2-methanidylpropane Chemical compound CC(C)[CH2-] RFONJRMUUALMBA-UHFFFAOYSA-N 0.000 description 1
- GMDYDZMQHRTHJA-UHFFFAOYSA-N 2-methyl-1-phenylpropan-1-ol Chemical compound CC(C)C(O)C1=CC=CC=C1 GMDYDZMQHRTHJA-UHFFFAOYSA-N 0.000 description 1
- WBPAQKQBUKYCJS-UHFFFAOYSA-N 2-methylpropyl 2-hydroxypropanoate Chemical compound CC(C)COC(=O)C(C)O WBPAQKQBUKYCJS-UHFFFAOYSA-N 0.000 description 1
- OIGWAXDAPKFNCQ-UHFFFAOYSA-N 4-isopropylbenzyl alcohol Chemical compound CC(C)C1=CC=C(CO)C=C1 OIGWAXDAPKFNCQ-UHFFFAOYSA-N 0.000 description 1
- NJESAXZANHETJV-UHFFFAOYSA-N 4-methylsalicylic acid Chemical compound CC1=CC=C(C(O)=O)C(O)=C1 NJESAXZANHETJV-UHFFFAOYSA-N 0.000 description 1
- KGYXYKHTHJPEBX-UHFFFAOYSA-N 5-ethoxy-3-ethoxycarbonyl-3-hydroxy-5-oxopentanoic acid Chemical compound CCOC(=O)CC(O)(CC(O)=O)C(=O)OCC KGYXYKHTHJPEBX-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YSAVZVORKRDODB-UHFFFAOYSA-N Diethyl tartrate Chemical compound CCOC(=O)C(O)C(O)C(=O)OCC YSAVZVORKRDODB-UHFFFAOYSA-N 0.000 description 1
- GYCKQBWUSACYIF-UHFFFAOYSA-N Ethyl salicylate Chemical compound CCOC(=O)C1=CC=CC=C1O GYCKQBWUSACYIF-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LDLDJEAVRNAEBW-UHFFFAOYSA-N Methyl 3-hydroxybutyrate Chemical compound COC(=O)CC(C)O LDLDJEAVRNAEBW-UHFFFAOYSA-N 0.000 description 1
- XYVQFUJDGOBPQI-UHFFFAOYSA-N Methyl-2-hydoxyisobutyric acid Chemical compound COC(=O)C(C)(C)O XYVQFUJDGOBPQI-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004791 alkyl magnesium halides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PCYQQSKDZQTOQG-NXEZZACHSA-N dibutyl (2r,3r)-2,3-dihydroxybutanedioate Chemical compound CCCCOC(=O)[C@H](O)[C@@H](O)C(=O)OCCCC PCYQQSKDZQTOQG-NXEZZACHSA-N 0.000 description 1
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical class Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- WIOHBOKEUIHYIC-UHFFFAOYSA-N diethyl 2,2-bis(hydroxymethyl)propanedioate Chemical compound CCOC(=O)C(CO)(CO)C(=O)OCC WIOHBOKEUIHYIC-UHFFFAOYSA-N 0.000 description 1
- OLLQYIBTJXUEEX-UHFFFAOYSA-N diethyl 3-hydroxypentanedioate Chemical compound CCOC(=O)CC(O)CC(=O)OCC OLLQYIBTJXUEEX-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- MRYSSTRVUMCKKB-UHFFFAOYSA-N ethyl 2-hydroxyhexanoate Chemical compound CCCCC(O)C(=O)OCC MRYSSTRVUMCKKB-UHFFFAOYSA-N 0.000 description 1
- MWSMNBYIEBRXAL-UHFFFAOYSA-N ethyl 3-hydroxybenzoate Chemical compound CCOC(=O)C1=CC=CC(O)=C1 MWSMNBYIEBRXAL-UHFFFAOYSA-N 0.000 description 1
- HYXRUZUPCFVWAH-UHFFFAOYSA-N ethyl 6-hydroxyhexanoate Chemical compound CCOC(=O)CCCCCO HYXRUZUPCFVWAH-UHFFFAOYSA-N 0.000 description 1
- SAXHIDRUJXPDOD-UHFFFAOYSA-N ethyl hydroxy(phenyl)acetate Chemical compound CCOC(=O)C(O)C1=CC=CC=C1 SAXHIDRUJXPDOD-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 229940005667 ethyl salicylate Drugs 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- MYEJNNDSIXAGNK-UHFFFAOYSA-N ethyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](CC)(OC(C)C)OC(C)C MYEJNNDSIXAGNK-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical group CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004678 hydrides Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- RIMIDGSPFGJFCN-UHFFFAOYSA-N hydroxymethyl benzoate Chemical compound OCOC(=O)C1=CC=CC=C1 RIMIDGSPFGJFCN-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ATCCIZURPPEVIZ-UHFFFAOYSA-N methyl 3-hydroxy-2-methylpropanoate Chemical compound COC(=O)C(C)CO ATCCIZURPPEVIZ-UHFFFAOYSA-N 0.000 description 1
- VBWFYEFYHJRJER-UHFFFAOYSA-N methyl 4-(hydroxymethyl)benzoate Chemical compound COC(=O)C1=CC=C(CO)C=C1 VBWFYEFYHJRJER-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- WSDQIHATCCOMLH-UHFFFAOYSA-N phenyl n-(3,5-dichlorophenyl)carbamate Chemical compound ClC1=CC(Cl)=CC(NC(=O)OC=2C=CC=CC=2)=C1 WSDQIHATCCOMLH-UHFFFAOYSA-N 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- KIWATKANDHUUOB-UHFFFAOYSA-N propan-2-yl 2-hydroxypropanoate Chemical compound CC(C)OC(=O)C(C)O KIWATKANDHUUOB-UHFFFAOYSA-N 0.000 description 1
- NJBNJRILTKLNQZ-UHFFFAOYSA-N propyl 4-hydroxybenzoate Chemical compound CCCOC(=O)C1=CC=C(O)C=C1.CCCOC(=O)C1=CC=C(O)C=C1 NJBNJRILTKLNQZ-UHFFFAOYSA-N 0.000 description 1
- 235000010232 propyl p-hydroxybenzoate Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229960003415 propylparaben Drugs 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- LYFHIDOIJPOKKR-UHFFFAOYSA-N tert-butyl 2-hydroxy-2-methylpropanoate Chemical compound CC(C)(C)OC(=O)C(C)(C)O LYFHIDOIJPOKKR-UHFFFAOYSA-N 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical class Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/08—Detecting, measuring or recording devices for evaluating the respiratory organs
- A61B5/091—Measuring volume of inspired or expired gases, e.g. to determine lung capacity
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/08—Detecting, measuring or recording devices for evaluating the respiratory organs
- A61B5/087—Measuring breath flow
- A61B5/0871—Peak expiratory flowmeters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
Definitions
- the present invention relates to a process for polymerization or copolymerization of ethylene, specifically to a process for polymerization or copolymerization of ethylene comprising the use of a solid complex titanium catalyst which is produced by reacting a magnesium compound solution with a mixture of a titanium compound and a silicon compound, washing the resulted a solid titanium catalyst component with a halogenated saturated hydrocarbon compound, and further reacting the resulted compound with a titanium compound.
- High catalyst activity, high bulk density of a polymer and the like are important factors to be considered in a catalyst when applying it to a liquid and a gas phase polymerization.
- a Ziegler - Natta type catalyst comprising magnesium for polymerization and copolymerization of ethylene is known to provide high catalyst activity and a polymer of high bulk density, and to be suitable for a liquid and a gas phase polymerization, thereby having been widely used in preparation of polyethylene.
- the object of the present invention is to provide a process for polymerization or copolymerization of ethylene in which the catalyst activity is superior and a polymer of high bulk density is provided, with the use of a catalyst obtained by a simple preparation process.
- the process for polymerization or copolymerization of ethylene according to the present invention comprises carrying out polymerization or copolymerization of ethylene in the presence of:
- the kinds of halogenated magnesium compound include di- halogenated magnesium such as magnesium chloride, magnesium iodide, magnesium fluoride and magnesium bromide; alkyl magnesium halides such as methylmagnesium halide, ethylmagnesium halide, propylmagnesium halide, butylmagnesium halide, isobutylmagnesium halide, hexylmagnesium halide and amylmagnesium halide; alkoxy magnesium halides such as methoxymagnesium halide, ethoxymagnesium halide, isopropoxymagnesium halide, butoxymagnesium halide and octoxymagnesium halide; and aryloxymagnesium halides such as phenoxymagnesium halide and methylphenoxymagnesium halide.
- the magnesium compound is preferred to be used as a mixture of two or more, and is also effective in the form of
- the above-listed compounds can be represented as a simple chemical formula. In some cases, however, they cannot be represented as a simple formula depending on the process for producing a magnesium compound. In such cases, it can be generally considered as a mixture of the listed magnesium compounds.
- the following compound may be used in the present invention: a compound which is obtained by reacting a magnesium compound with a polysiloxane compound, a halogen-containing silane compound, an ester, an alcohol or the like; and a compound which is obtained by reacting metal magnesium with an alcohol, phenol or ether in the presence of a halosilane, phosphoric(V) chloride or thionyl chloride.
- Preferred magnesium compounds include magnesium halides, particularly magnesium chloride, alkylmagnesium chloride, preferably having Cl-10 alkyl group, alkoxy- magnesium chloride, preferably having Cl-10 alkoxy group, and aryloxymagnesium chloride, preferably having C6-20 aryloxy group.
- the magnesium compound solution can be prepared by formulating one of the foregoing magnesium compounds to a solution with the use of an alcohol as a solvent, in the presence or absence of a hydrocarbon solvent.
- the hydrocarbon solvent which can be used herein includes: aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and kerosene; alicyclic hydrocarbons such as cyclopentane, methylcy- clopentane, cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenezne, cumene and cymene; and halogenated hydrocarbons such as dichloropropane, dichloroethylene, trichloroethylene, tetra- chlorocarbon and chlorobenzene.
- the alcohols which can be used herein include alcohols having Cl - 20 such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, dodecanol, octade- cylalcohol, benzylalcohol, phenylethylalcohol, isopropylbenzylalcohol and cumylalcohol.
- Preferred alcohols are those having Cl - 12.
- the desired average size of a catalyst and the particle size distribution may vary upon the kinds and total amount of an alcohol, kinds of a magnesium compound, the ratio of magnesium and alcohol and the like, the total amount of the alcohol used to prepare a magnesium compound solution is desirably at least 0.5 mol, preferably about 1.0 - 20 mol, and more preferably about 2.0 - 10 mol, per mol of the magnesium compound.
- the reaction between a magnesium compound and an alcohol in preparing a magnesium compound solution is preferably carried out in a hydrocarbon medium, and the reaction is desirably carried out at the temperature of - 25 °C or higher, preferably
- ester compound having at least one hydroxyl group used in the above step (ii) the following compounds can be used: unsaturated fatty acid esters having at least one hydroxyl group such as 2 - hydroxy ethylacrylate, 2 - hydroxy ethyl- methacrylate, 2 - hydroxy propylacrylate, 2 - hydroxy propylmethacrylate, 4 - hydoxy butylacrylate and pentaerythritol triacrylate; aliphatic monoesters or polyesters having at least one hydroxyl group such as 2 - hydroxy ethyl acetate, methyl 3 - hydroxy butyrate, ethyl 3 - hydroxy butyrate, methyl 2 - hydroxy isobutyrate, ethyl 2
- one or more compounds such as, for example, dimethyldimethoxy silane, dimethyldiethoxy silane, diphenyldimethoxy silane, methylphenyldimethoxy silane, diphenyldiethoxy silane, ethyltrimethoxy silane, vinyltrimethoxy silane, methyltrimethoxy silane, phenyltrimethoxy silane, methyl- triethoxy silane, ethyltriethoxy silane, vinyltriethoxy silane, butyltriethoxy silane, phenyltriethoxy silane, ethyltriisopropoxy silane, vinyltributoxy silane, tetraethoxy silane, ethyl silicate, butyl silicate and methyltriaryloxy silane can be used.
- the amount of the silicon compound having at least one alkoxy group is preferably 0.05-3 mol, and more preferably 0.1-2 mol, per mol of the magnesium compound
- the reaction temperature for the contact reaction between a liquid magnesium compound solution with an ester compound having at least one hydroxyl group and an alkoxy silicon compound is preferably 0-100°C, and more preferably 10-70°C.
- the magnesium compound solution reacted with electron donors are further reacted with a mixture of a liquid titanium compound represented by the general formula of Ti(OR) a X 4-a , in which R is a hydrocarbon group; X is a halogen atom; and a is an integer of 0-4, and a silicon compound represented by the general formula of R n SiCl 4— n , in which R is a hydrogen atom, an alkyl group having Cl-IO, alkoxy, haloalkyl, aryl group, or halosilyl group having Cl -8 or halosilylalkyl group; and n is an integer of 0-3, so as to recrystallize catalyst particles.
- titanium compound is a halogen - containing titanium compound, and more preferred is a titanium tetrachloride.
- the silicon compounds of the general formula R n SiCl 4-n include: silicon tetrachloride; trichlorosilanes such as methyltrichlorosilane, ethyltrichlorosilane and phenyltrichlorosilane; dichlorosilanes such as dimethyldichlorosilane, di- ethyldichlorosilane, diphenyldichlorosilane and methylphenyldichlorosilane; monochlrorosilanes such as trimethylchlrorosilane. Mixtures of the above-listed silicon compounds may also be used in the present invention.
- Preferred silicon compound is silicon tetrachloride.
- the amount of the mixture of a titanium compound and a silicon compound used for the recrystallization of a magnesium compound solution is suitably 0.1 - 200 mol, preferably 0.1 - 100 mol, and more preferably 0.2 - 80 mol, per mol of the magnesium compound.
- the molar ratio of the silicon compound to the titanium compound is preferably 0.05-0.95, and more preferably 0.1-0.8.
- the shape and size of the recrystallized solid component vary depending on the reaction conditions when reacting the magnesium compound solution with the mixture of a titanium compound and a silicon compound. Therefore, it is desirable to carry out the reaction between the magnesium compound solution and the mixture of a titanium compound and a silicon compound at sufficiently low temperature to form a solid component.
- the contact reaction is preferably carried out at - 70-70°C, and more preferably at - 50-50°C. After the contact reaction, the reaction temperature was gradually elevated to 50-150°C for sufficient reaction for 0.5-5 hours.
- the temperature during the washing process is 10-120°C, and preferably 20-100°C.
- the solid catalyst particle obtained from the step (iv) is further reacted with a titanium compound.
- the titanium compound used in step(v) is compounds represented by the general formula Ti(OR) X , in which R is a hy- a 4-a drocarbon group; X is a halogen atom; and a is an integer of 0 - 4, and is preferably a titanium halide and halogenated alkoxy titanium of which the alkoxy group has 1 - 20 carbon atoms and more preferably titanium tetrachloride.
- the amount of the titanium compound is used in step(v) is suitably 1 -20 mol, and preferably 1-10 mol, per mol of the magnesium compound.
- the reaction is preferably carried out in the temperature range of 40-150°C for 0.5-5 hours.
- the (a) solid complex titanium catalyst can be used in prepolymerization of ethylene or ⁇ -olefin, before being used as an element for (co)polymerization.
- Prepolymerization can be carried out in the presence of said catalyst and an organoaluminum compound such as triethylaluminum in a hydrocarbon solvent such as hexane, under the conditions of sufficiently low temperature and pressure.
- the prepolymerization helps the catalyst maintain its shape by surrounding the catalyst particles with polymers, thereby improving the polymer morphology after polymerization.
- the weight ratio of polymer/ /catalyst, after prepolymerization is 0.1 - 20:1.
- the polymerization or copolymerization of ethylene process of the present invention is conducted by using a catalyst system comprising (a) a solid complex titanium catalyst prepared as described above, and (b) an organometallic compound from Group II or in of the Periodic table of elements.
- the catalyst (a) is advantageously used in homopolymerization of ethylene and copolymerization of ethylene with ⁇ -olefins which have 3 or more carbon atoms, such as propylene, 1 - butene, 1 - pentene, 4 - methyl - 1 - pentene and 1 - hexene.
- the organometallic compound (b) useful in the present invention is represented by the general formula of MR n , wherein M is a metal component from Group II or IIIA of the Periodic table of elements such as magnesium, calcium, zinc, boron, aluminum and gallium; and R is an alkyl group having Cl - 20 such as methyl, ethyl, butyl, hexyl, octyl and decyl; and n is the atomic valence of the metal component. More preferred organometallic compound is trialkylaluminum compounds having Cl - 6 such as tri- ethylaluminum and triisobutylaluminum and the mixtures thereof.
- organoaluminum compounds comprising one or more halogens or hydride groups such as ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride and diisobutylaluminum hydride may be used.
- Polymerization can be carried out by a gas phase or a bulk polymerization in the absence of an organic solvent, or by a liquid slurry polymerization in the presence of an organic solvent.
- the concentration of the solid complex titanium catalyst (a) in the polymerization reaction system is, based on titanium atoms of the catalyst in IL solvent, about 0.001-5 mmol, preferably about 0.001-1.0 mmol, and more preferably about 0.01-0.5 mmol.
- the concentration of the organometallic compound (b) in the polymerization reaction system is, calculated as metal atoms, about 1-2,000 mol, preferably about 5-500 per mol of a titanium atom in the catalyst.
- the solvent is preferably a non - polar organic solvent including alkane compounds such as hexane, n - heptane, octane, nonane and decane, and aromatic compounds such as cycloalkane, and more preferably hexane. These solvents are preferred to be purified before its use, in order not to affect to the catalyst activity.
- the concentration of the solid complex titanium catalyst (a) in the polymerization system is, based on titanium atoms of the catalyst in IL solvent, about 0.001-5 mmol, and preferably 0.001-0.5 mmol.
- the polymerization reaction is carried out at sufficiently high temperature regardless of the types of polymerization process, for achieving high polymerization rate.
- the reaction temperature is about 20-200°C, and more preferably about 20-95°C.
- the pressure of monomers during polymerization is preferably 1 - 100 atm., and more preferably 2-50 atm..
- the molecular weight is represented as melting index (MI;
- a solid complex titanium catalyst was prepared by the following steps.
- a autocrave reactor having 2 L volume was dried in an oven and assembled while it was still hot.
- the atmosphere inside the reactor was substituted with nitrogen by alternately applying nitrogen and vacuum three times.
- 1,000 ml of dried n - hexane, 3 mmol of triethylaluminum, 0.03 mmol of a solid complex titanium catalyst, based on the titanium atom and 1,000 ml of hydrogen were subsequently added in this order to the reactor.
- a stirrer was operated at a constant speed of 700 rpm.
- the temperature of the reactor was elevated to 80°C, and the pressure of ethylene was adjusted to 80 psi. Then polymerization was carried out over 1 hour.
- the temperature of the reactor was lowered to room temperature, and excessive amount of an ethanol solution was added to the polymerized product so as to terminate the reaction.
- the resulted polymers were filtered for separation, collected and dried in a vacuum oven at 50°C for 6 hours or more to obtain polyethylene as a white powder.
- the polymerization activity (kg polyethylene/ g catalyst) was calculated as the weight (kg) of the obtained polymers per the amount (g) of a catalyst used therein, and it is represented in the following Table 1 together with other results of MI (g/10 minutes), bulk density (BD) (Mw/Mn) and loading amount (wt%).
- a catalyst was prepared by the same process as in Example 1, except that the washing process was repeated twice in the step (iv) of the preparation of catalyst in Example 1. Polymerization was carried out as in Example 1. The results were represented in the following Table 1.
- a catalyst was prepared by the same process as in Example 1, except that the washing process was performed only once in the step (iv) of the preparation of catalyst in Example 1. Polymerization was carried out as in Example 1. The results were represented in the following Table 1.
- a catalyst was prepared by the same process as in Example 1, except that the washing process was carried out at 25°C in the step (iv) of the preparation of catalyst in Example 1. Polymerization was carried out as in Example 1. The results were represented in the following Table 1.
- a catalyst was prepared by the same process as in Example 1, except that the washing process was carried out at 40°C in the step (iv) of the preparation of catalyst in Example 1. Polymerization was carried out as in Example 1. The results were represented in the following Table 1.
- a catalyst was prepared by the same process as in Example 1, except that the step (iv) of the catalyst preparation in Example 1 was not carried out. Polymerization was carried out as in Example 1. The results were represented in the following Table 1.
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Abstract
Provided is a process for polymerization and copolymerization of ethylene, specifically comprising carrying out polymerization or copolymerization ethylene in the presence of (a) a solid complex titanium catalyst which is produced by the process comprising: (i) preparing a magnesium compound solution by contacting a halogenated magnesium compound and an alcohol for allowing a reaction; (ii) reacting the resulted magnesium compound solution with an ester compound having at least one hydroxyl group and a silicon compound having at least one alkoxy group; (iii) reacting the resulted solution with a mixture of a titanium compound and a silicon compound to obtain a solid titanium catalyst component; (iv) washing the resulted solid titanium catalyst component with a halogenated saturated hydrocarbon compound; and (v) further reacting the washed solid titanium catalyst component with a titanium compound to obtain a solid complex titanium catalyst, and (b) an organometallic compound from Group II or III of Periodic table.of elements. According to the present invention, it is possible to provide a process for polymerization or copolymerization of ethylene in which the catalyst activity is improved and a polymer of high bulk density is provided, with the use of a catalyst prepared by a simple process.
Description
Description PROCESS FOR POLYMERIZATION OR COPOLY-
MERIZATION OF ETHYLENE
Technical Field
[1] The present invention relates to a process for polymerization or copolymerization of ethylene, specifically to a process for polymerization or copolymerization of ethylene comprising the use of a solid complex titanium catalyst which is produced by reacting a magnesium compound solution with a mixture of a titanium compound and a silicon compound, washing the resulted a solid titanium catalyst component with a halogenated saturated hydrocarbon compound, and further reacting the resulted compound with a titanium compound.
Background Art
[2] High catalyst activity, high bulk density of a polymer and the like are important factors to be considered in a catalyst when applying it to a liquid and a gas phase polymerization. A Ziegler - Natta type catalyst comprising magnesium for polymerization and copolymerization of ethylene is known to provide high catalyst activity and a polymer of high bulk density, and to be suitable for a liquid and a gas phase polymerization, thereby having been widely used in preparation of polyethylene.
[3] Processs for producing many titanium - based catalysts comprising magnesium for olefin polymerization have been reported. Especially, processs using a magnesium solution for obtaining a catalyst for polymerizing olefin with high bulk density have been widely known. For such examples, there have been processs for obtaining a magnesium solution by reacting a magnesium compound with an electron donor such as alcohol, amine, cyclic ether, organic carboxylic acid or the like, in the presence of a hydrocarbon solvent. Specifically, processs using an alcohol as an electron donor are disclosed in US patent Nos. 4,330,649 and 5,106,807. Further, a process for producing a magnesium - supported catalyst by reacting such magnesium solution with a halogen - containing compound such as titanium tetrachloride is also well known in the art. Alternatively, there have been efforts to adjust the polymerization activity or molecular weight distribution of a polymer by using ester compounds in preparation of a catalyst.
[4] However, these catalysts still need to be further improved in terms of catalyst activity, although they can provide high bulk density.
[5] In consideration of improvement in catalyst activity, there have been US patent
Nos. 4,477,639 and 4,518,706, in which a cyclic ether, tetrahydrofuran is used as a solvent for a magnesium compound. In US Patent Nos. 4,847,227, 4,816,433, 4,829,037, 4,970,186 and 5,130,284, a catalyst for olefin polymerization which
provides excellent polymerization activity and a polymer of high bulk density is disclosed, by reacting an electron donor such as magnesium alkoxide, dialkylphthalate, phthaloylchloride or the like with a titanium chloride compound. However, there still has been a need for a process for producing a catalyst for polymerization and copoly- merization of ethylene which is more convenient and simpler, and can provide high catalyst activity and a polymer of high bulk density. Disclosure of Invention
Technical Problem
[6] However, these catalysts still need to be further improved in terms of catalyst activity, although they can provide high bulk density.
[7] In consideration of improvement in catalyst activity, there have been US patent
Nos. 4,477,639 and 4,518,706, in which a cyclic ether, tetrahydrofuran is used as a solvent for a magnesium compound. In US Patent Nos. 4,847,227, 4,816,433, 4,829,037, 4,970,186 and 5,130,284, a catalyst for olefin polymerization which provides excellent polymerization activity and a polymer of high bulk density is disclosed, by reacting an electron donor such as magnesium alkoxide, dialkylphthalate, phthaloylchloride or the like with a titanium chloride compound. However, there still has been a need for a process for producing a catalyst for polymerization and copoly- merization of ethylene which is more convenient and simpler, and can provide high catalyst activity and a polymer of high bulk density.
Technical Solution
[8] The object of the present invention is to provide a process for polymerization or copolymerization of ethylene in which the catalyst activity is superior and a polymer of high bulk density is provided, with the use of a catalyst obtained by a simple preparation process.
[9] The process for polymerization or copolymerization of ethylene according to the present invention comprises carrying out polymerization or copolymerization of ethylene in the presence of:
[10] (a) a solid complex titanium catalyst which is produced by the process comprising:
[11] (i) preparing a magnesium compound solution by contacting a halogenated magnesium compound and an alcohol;
[12] (ii) reacting the resulted magnesium compound solution with an ester compound having at least one hydroxyl group and a silicon compound having at least one alkoxy group ;
[13] (iii) reacting the resulted solution with a mixture of a titanium compound and a silicon compound to obtain a solid titanium catalyst component;
[14] (iv) washing the resulted solid titanium catalyst component with a halogenated
saturated hydrocarbon compound; and
[15] (v) further reacting the washed solid titanium catalyst component with a titanium compound to obtain a solid complex titanium catalyst, and
[16] (b) an organometallic compound from Group II or in of Periodic table of elements.
[17] In the above step (i), the kinds of halogenated magnesium compound include di- halogenated magnesium such as magnesium chloride, magnesium iodide, magnesium fluoride and magnesium bromide; alkyl magnesium halides such as methylmagnesium halide, ethylmagnesium halide, propylmagnesium halide, butylmagnesium halide, isobutylmagnesium halide, hexylmagnesium halide and amylmagnesium halide; alkoxy magnesium halides such as methoxymagnesium halide, ethoxymagnesium halide, isopropoxymagnesium halide, butoxymagnesium halide and octoxymagnesium halide; and aryloxymagnesium halides such as phenoxymagnesium halide and methylphenoxymagnesium halide. The magnesium compound is preferred to be used as a mixture of two or more, and is also effective in the form of a complex with other metals.
[18] In most cases, the above-listed compounds can be represented as a simple chemical formula. In some cases, however, they cannot be represented as a simple formula depending on the process for producing a magnesium compound. In such cases, it can be generally considered as a mixture of the listed magnesium compounds. For example, the following compound may be used in the present invention: a compound which is obtained by reacting a magnesium compound with a polysiloxane compound, a halogen-containing silane compound, an ester, an alcohol or the like; and a compound which is obtained by reacting metal magnesium with an alcohol, phenol or ether in the presence of a halosilane, phosphoric(V) chloride or thionyl chloride. Preferred magnesium compounds include magnesium halides, particularly magnesium chloride, alkylmagnesium chloride, preferably having Cl-10 alkyl group, alkoxy- magnesium chloride, preferably having Cl-10 alkoxy group, and aryloxymagnesium chloride, preferably having C6-20 aryloxy group.
[19] The magnesium compound solution can be prepared by formulating one of the foregoing magnesium compounds to a solution with the use of an alcohol as a solvent, in the presence or absence of a hydrocarbon solvent. The hydrocarbon solvent which can be used herein includes: aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and kerosene; alicyclic hydrocarbons such as cyclopentane, methylcy- clopentane, cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenezne, cumene and cymene; and halogenated hydrocarbons such as dichloropropane, dichloroethylene, trichloroethylene, tetra- chlorocarbon and chlorobenzene.
[20] When converting the magnesium compound into a magnesium compound solution,
it is preferred to use an alcohol in the presence of the foregoing hydrocarbon. The alcohols which can be used herein include alcohols having Cl - 20 such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, dodecanol, octade- cylalcohol, benzylalcohol, phenylethylalcohol, isopropylbenzylalcohol and cumylalcohol. Preferred alcohols are those having Cl - 12. Although the desired average size of a catalyst and the particle size distribution may vary upon the kinds and total amount of an alcohol, kinds of a magnesium compound, the ratio of magnesium and alcohol and the like, the total amount of the alcohol used to prepare a magnesium compound solution is desirably at least 0.5 mol, preferably about 1.0 - 20 mol, and more preferably about 2.0 - 10 mol, per mol of the magnesium compound. [21] The reaction between a magnesium compound and an alcohol in preparing a magnesium compound solution is preferably carried out in a hydrocarbon medium, and the reaction is desirably carried out at the temperature of - 25 °C or higher, preferably
- 10 - 200 °C , and more preferably around 0 - 150 °C for 15 minutes to 5 hours and preferably for 30 minutes to 4 hours, though the reaction temperature may vary according to the kinds and amount of an alcohol used.
[22] As for the ester compound having at least one hydroxyl group used in the above step (ii), the following compounds can be used: unsaturated fatty acid esters having at least one hydroxyl group such as 2 - hydroxy ethylacrylate, 2 - hydroxy ethyl- methacrylate, 2 - hydroxy propylacrylate, 2 - hydroxy propylmethacrylate, 4 - hydoxy butylacrylate and pentaerythritol triacrylate; aliphatic monoesters or polyesters having at least one hydroxyl group such as 2 - hydroxy ethyl acetate, methyl 3 - hydroxy butyrate, ethyl 3 - hydroxy butyrate, methyl 2 - hydroxy isobutyrate, ethyl 2
- hydroxy isobutyrate, methyl - 3 - hydroxy - 2 - methyl propionate, 2,2 - dimethyl
- 3 - hydroxy propionate, ethyl - 6 - hydroxy hexanoate, t - butyl - 2 - hydroxy isobutyrate, diethyl - 3 - hydroxy glutarate, ethyl lactate, isopropyl lactate, butyl isobutyl lactate, isobutyl lactate, ethyl mandelate, dimethyl ethyl tartrate, ethyl tartrate, dibutyl tartrate, diethyl citrate, triethyl citrate, ethyl 2 - hydroxy caproate and diethyl bis - (hydroxy methyl)malonate; aromatic esters having at least one hydroxyl group such as 2 - hydroxy ethyl benzoate, 2 - hydroxy ethyl salicylate, methyl 4 - (hydroxymethyl)benzoate, methyl 4 - hydroxy benzoate, ethyl 3 - hydroxy benzoate, 4 - methyl salicylate, ethyl salicylate, phenyl salicylate, propyl 4 - hydroxy benzoate, phenyl 3 - hydroxy naphthanoate, monoethylene glycol mono benzoate, diethylene glycol monobenzoate and Methylene glycol monobenzoate; and alicyclic esters having at least one hydroxyl group such as hydroxy butyl lactone. The amount of the ester compound having at least one hydroxyl group is 0.001 - 5 mol, and preferably 0.01 - 2 mol per mol of magnesium.
[23] As for the silicon compound having at least one alkoxy group, which is another
electron donor used in the above step (ii), compounds having the general formula of R n
Si(OR) , wherein R is a hydrocarbon group having Cl - 12, and n is an integer of 0
4-n
- 3, are preferred. Specifically, one or more compounds such as, for example, dimethyldimethoxy silane, dimethyldiethoxy silane, diphenyldimethoxy silane, methylphenyldimethoxy silane, diphenyldiethoxy silane, ethyltrimethoxy silane, vinyltrimethoxy silane, methyltrimethoxy silane, phenyltrimethoxy silane, methyl- triethoxy silane, ethyltriethoxy silane, vinyltriethoxy silane, butyltriethoxy silane, phenyltriethoxy silane, ethyltriisopropoxy silane, vinyltributoxy silane, tetraethoxy silane, ethyl silicate, butyl silicate and methyltriaryloxy silane can be used. The amount of the silicon compound having at least one alkoxy group is preferably 0.05-3 mol, and more preferably 0.1-2 mol, per mol of the magnesium compound.
[24] The reaction temperature for the contact reaction between a liquid magnesium compound solution with an ester compound having at least one hydroxyl group and an alkoxy silicon compound is preferably 0-100°C, and more preferably 10-70°C.
[25] In the step (iii), the magnesium compound solution reacted with electron donors are further reacted with a mixture of a liquid titanium compound represented by the general formula of Ti(OR) a X 4-a , in which R is a hydrocarbon group; X is a halogen atom; and a is an integer of 0-4, and a silicon compound represented by the general formula of R n SiCl 4— n , in which R is a hydrogen atom, an alkyl group having Cl-IO, alkoxy, haloalkyl, aryl group, or halosilyl group having Cl -8 or halosilylalkyl group; and n is an integer of 0-3, so as to recrystallize catalyst particles. In the above general formula, R is preferably an alkyl group having Cl-10. [26] The titanium compounds of the general formula Ti(OR) X include: tetra- a 4-a halogenated titanium such as TiCl , TiBr and TiI ; trihalogenated alkoxytitanium such as Ti(OCH3)Cl3, Ti(OC2H5)Cl3, Ti(OC2H5)Br3 and Ti(O(i-C4H9))Br3; dihalogenated alkoxytitanium such as Ti(OCH 3 ) 2 Cl 2 , Ti(OC 2 H 5 ) 2 Cl 2 , Ti(O(i-C 4 H 9 )) 2 Cl 2 and Ti(OC 2 H 5
) Br ; tetraalkoxytitanium such as Ti(OCH ) , Ti(OC H ) and Ti(OC H ) . Mixtures of the above - listed titanium compounds may also be used in the present invention. Preferred titanium compound is a halogen - containing titanium compound, and more preferred is a titanium tetrachloride. [27] The silicon compounds of the general formula R n SiCl 4-n include: silicon tetrachloride; trichlorosilanes such as methyltrichlorosilane, ethyltrichlorosilane and phenyltrichlorosilane; dichlorosilanes such as dimethyldichlorosilane, di- ethyldichlorosilane, diphenyldichlorosilane and methylphenyldichlorosilane; monochlrorosilanes such as trimethylchlrorosilane. Mixtures of the above-listed silicon compounds may also be used in the present invention. Preferred silicon compound is silicon tetrachloride. [28] The amount of the mixture of a titanium compound and a silicon compound used
for the recrystallization of a magnesium compound solution is suitably 0.1 - 200 mol, preferably 0.1 - 100 mol, and more preferably 0.2 - 80 mol, per mol of the magnesium compound. The molar ratio of the silicon compound to the titanium compound is preferably 0.05-0.95, and more preferably 0.1-0.8. The shape and size of the recrystallized solid component vary depending on the reaction conditions when reacting the magnesium compound solution with the mixture of a titanium compound and a silicon compound. Therefore, it is desirable to carry out the reaction between the magnesium compound solution and the mixture of a titanium compound and a silicon compound at sufficiently low temperature to form a solid component. The contact reaction is preferably carried out at - 70-70°C, and more preferably at - 50-50°C. After the contact reaction, the reaction temperature was gradually elevated to 50-150°C for sufficient reaction for 0.5-5 hours.
[29] The kinds of the halogenated saturated hydrocarbon compounds used in the step
(iv) include compounds with Cl - 10 comprising one or more halogens including chlorine, bromine, fluorine and iodine, such as ethyldichloride, chloroform, tert - butyl chloride, tetrachloromethane, ethylbromide, tert - butyliodide, n - butylbromide, n - butyliodide and n - butylfluoride, and preferred is ethyldichloride. Mixtures of one or more said halogenated saturated hydrocarbon can be used in the present invention.
[30] The washing process by using the halogenated saturated hydrocarbon is carried out
1-5 times, and preferably 1-3 times. The temperature during the washing process is 10-120°C, and preferably 20-100°C.
[31] In the step (v), the solid catalyst particle obtained from the step (iv) is further reacted with a titanium compound. The titanium compound used in step(v) is compounds represented by the general formula Ti(OR) X , in which R is a hy- a 4-a drocarbon group; X is a halogen atom; and a is an integer of 0 - 4, and is preferably a titanium halide and halogenated alkoxy titanium of which the alkoxy group has 1 - 20 carbon atoms and more preferably titanium tetrachloride.
[32] The amount of the titanium compound is used in step(v) is suitably 1 -20 mol, and preferably 1-10 mol, per mol of the magnesium compound. The reaction is preferably carried out in the temperature range of 40-150°C for 0.5-5 hours.
[33] The (a) solid complex titanium catalyst can be used in prepolymerization of ethylene or α-olefin, before being used as an element for (co)polymerization. Prepolymerization can be carried out in the presence of said catalyst and an organoaluminum compound such as triethylaluminum in a hydrocarbon solvent such as hexane, under the conditions of sufficiently low temperature and pressure. The prepolymerization helps the catalyst maintain its shape by surrounding the catalyst particles with polymers, thereby improving the polymer morphology after polymerization. The weight ratio of polymer/ /catalyst, after prepolymerization is 0.1 - 20:1.
[34] The polymerization or copolymerization of ethylene process of the present invention is conducted by using a catalyst system comprising (a) a solid complex titanium catalyst prepared as described above, and (b) an organometallic compound from Group II or in of the Periodic table of elements. Particularly, the catalyst (a) is advantageously used in homopolymerization of ethylene and copolymerization of ethylene with α-olefins which have 3 or more carbon atoms, such as propylene, 1 - butene, 1 - pentene, 4 - methyl - 1 - pentene and 1 - hexene.
[35] The organometallic compound (b) useful in the present invention is represented by the general formula of MR n , wherein M is a metal component from Group II or IIIA of the Periodic table of elements such as magnesium, calcium, zinc, boron, aluminum and gallium; and R is an alkyl group having Cl - 20 such as methyl, ethyl, butyl, hexyl, octyl and decyl; and n is the atomic valence of the metal component. More preferred organometallic compound is trialkylaluminum compounds having Cl - 6 such as tri- ethylaluminum and triisobutylaluminum and the mixtures thereof. Optionally, organoaluminum compounds comprising one or more halogens or hydride groups such as ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride and diisobutylaluminum hydride may be used.
[36] Polymerization can be carried out by a gas phase or a bulk polymerization in the absence of an organic solvent, or by a liquid slurry polymerization in the presence of an organic solvent.
[37] In gas phase polymerization, the concentration of the solid complex titanium catalyst (a) in the polymerization reaction system is, based on titanium atoms of the catalyst in IL solvent, about 0.001-5 mmol, preferably about 0.001-1.0 mmol, and more preferably about 0.01-0.5 mmol. The concentration of the organometallic compound (b) in the polymerization reaction system is, calculated as metal atoms, about 1-2,000 mol, preferably about 5-500 per mol of a titanium atom in the catalyst.
[38] In liquid slurry polymerization, the solvent is preferably a non - polar organic solvent including alkane compounds such as hexane, n - heptane, octane, nonane and decane, and aromatic compounds such as cycloalkane, and more preferably hexane. These solvents are preferred to be purified before its use, in order not to affect to the catalyst activity. The concentration of the solid complex titanium catalyst (a) in the polymerization system is, based on titanium atoms of the catalyst in IL solvent, about 0.001-5 mmol, and preferably 0.001-0.5 mmol.
[39] The polymerization reaction is carried out at sufficiently high temperature regardless of the types of polymerization process, for achieving high polymerization rate. Generally, the reaction temperature is about 20-200°C, and more preferably about 20-95°C. The pressure of monomers during polymerization is preferably 1 - 100 atm., and more preferably 2-50 atm..
[40] In the present invention, the molecular weight is represented as melting index (MI;
230 °C, 2.16kg)(ASTM D 1238), which is a generally known unit for molecular weight in this field of art. Generally, the lower the molecular weight, the bigger the MI value.
Mode for Invention
[41] Hereinafter, the present invention is further described in detail, referencing the following examples. However, the scope of the present invention is by no means limited by these examples which have only illustrative purposes.
[42] Examples
[43] Example 1
[44] Preparation of catalyst
[45] A solid complex titanium catalyst was prepared by the following steps.
[46] (i) Preparation of a magnesium compound solution
[47] 9.5g of MgCl and 600 ml of decane were added into a 1.0 L reactor equipped with a mechanical stirrer, of which atmosphere was substituted with nitrogen, and then the mixture was stirred at 500 rpm. Then, after 70 ml of 2 - ethylhexanol was added thereto, the temperature was elevated to 120°C for allowing the reaction for 3 hours. After the reaction, the resulted homogenous solution was cooled to room temperature (25°C).
[48] (ii) Contact reaction between the magnesium compound solution with ester having a hydroxyl group and an alkoxy silane compound
[49] To the magnesium compound solution cooled to 25°C, 0.8 ml of 2 - hydroxyethyl methacrylate and 15.0 ml of tetraethoxy silane were added and the mixture was allowed for reaction for 1 hour.
[50] (iii) Treating the solution with a mixture of a titanium compound and a silicon compound
[51] The resulted solution was adjusted to room temperature(25°C), a mixture of 50 ml of titanium tetrachloride and 50 ml of silicon tetrachloride was added dropwise over 1 hour. Completing the addition, the temperature of the reactor was elevated to 70°C and maintained for 1 hour. After lowering the temperature of the reactor to 60°C, the upper phase of the solution was separated out.
[52] (iv) Washing the resulted catalyst component with a halogenated saturated hydrocarbon compound
[53] To the remained solid phase, 400 ml of ethyldichloride were added, then the temperature was raised to 60°C and the resulted mixture was stirred. Stirring was halted to separate the upper phase of the solution. This process was repeated three ti mes.
[54] (v) Reaction with a titanium compound
[55] 300 ml of decane and 100 ml of titanium tetrachloride were added thereto, and the
temperature was elevated to 100°C and maintained for 2 hours. Then, the reactor was cooled to the room temperature and 400 ml of hexane were added to the reactor for washing, until the unreacted free titanium tetrachloride was removed. The titanium content in the resulted solid complex titanium catalyst was 5.5 wt%.
[56] Polymerization
[57] A autocrave reactor having 2 L volume was dried in an oven and assembled while it was still hot. The atmosphere inside the reactor was substituted with nitrogen by alternately applying nitrogen and vacuum three times. 1,000 ml of dried n - hexane, 3 mmol of triethylaluminum, 0.03 mmol of a solid complex titanium catalyst, based on the titanium atom and 1,000 ml of hydrogen were subsequently added in this order to the reactor. A stirrer was operated at a constant speed of 700 rpm. The temperature of the reactor was elevated to 80°C, and the pressure of ethylene was adjusted to 80 psi. Then polymerization was carried out over 1 hour. After completing polymerization, the temperature of the reactor was lowered to room temperature, and excessive amount of an ethanol solution was added to the polymerized product so as to terminate the reaction. The resulted polymers were filtered for separation, collected and dried in a vacuum oven at 50°C for 6 hours or more to obtain polyethylene as a white powder.
[58] The polymerization activity (kg polyethylene/ g catalyst) was calculated as the weight (kg) of the obtained polymers per the amount (g) of a catalyst used therein, and it is represented in the following Table 1 together with other results of MI (g/10 minutes), bulk density (BD) (Mw/Mn) and loading amount (wt%).
[59] Example 2
[60] A catalyst was prepared by the same process as in Example 1, except that the washing process was repeated twice in the step (iv) of the preparation of catalyst in Example 1. Polymerization was carried out as in Example 1. The results were represented in the following Table 1.
[61] Example 3
[62] A catalyst was prepared by the same process as in Example 1, except that the washing process was performed only once in the step (iv) of the preparation of catalyst in Example 1. Polymerization was carried out as in Example 1. The results were represented in the following Table 1.
[63] Example 4
[64] A catalyst was prepared by the same process as in Example 1, except that the washing process was carried out at 25°C in the step (iv) of the preparation of catalyst in Example 1. Polymerization was carried out as in Example 1. The results were represented in the following Table 1.
[65] Example 5
[66] A catalyst was prepared by the same process as in Example 1, except that the
washing process was carried out at 40°C in the step (iv) of the preparation of catalyst in Example 1. Polymerization was carried out as in Example 1. The results were represented in the following Table 1.
[67] Comparative example 1
[68] A catalyst was prepared by the same process as in Example 1, except that the step (iv) of the catalyst preparation in Example 1 was not carried out. Polymerization was carried out as in Example 1. The results were represented in the following Table 1.
[69]
Table 1
Industrial Applicability
[70] According to the present invention, it is possible to provide a process for polymerization of copolymerization of ethylene in which the catalyst activity is superior, and high bulk density is provided by the use of a catalyst obtained by a simple preparation process.
Claims
[1] L A process for polymerizing or copolymerizing ethylene comprising carrying out polymerization or copolymerization of ethylene in the presence of (a) and (b):
(a) a solid complex titanium catalyst which is produced by the process comprising:
(i) preparing a magnesium compound solution by contacting a halogenated magnesium compound and an alcohol;
(ii) reacting the resulted magnesium compound solution with an ester compound having at least one hydroxyl group and a silicon compound having at least one alkoxy group ;
(iii) reacting the resulted solution with a mixture of a titanium compound and a silicon compound to obtain a solid titanium catalyst component;
(iv) washing the resulted solid titanium catalyst component with a halogenated saturated hydrocarbon compound; and
(v) further reacting the washed solid titanium catalyst component with a titanium compound to obtain a solid complex titanium catalyst, and
(b) an organometallic compound from Group II or HI of Periodic table of elements.
[2] 2. The process for polymerizing or copolymerizing ethylene according to claim
1, wherein the ester compound having at least one hydroxyl group is selected from the group consisting of unsaturated fatty acid esters having at least one hydroxyl group, aliphatic monoesters or polyesters having at least one hydroxyl group, aromatic esters having at least one hydroxyl group, and alicyclic esters having at least one hydroxyl group; and the silicon compound having at least one alkoxy group is at least one selected from alkoxy silane compounds represented by the general formula of R n Si(OR) 4— n , wherein R is a hydrocarbon group having
Cl - 12, and n is an integer of 0 - 3.
[3] 3. The process for polymerizing or copolymerizing ethylene according to claim
1, wherein the titanium compound and the silicon compound are represented by each general formula of Ti(OR) X , in which R is a hydrocarbon group; X is a a 4-a halogen atom; and a is an integer of 0 - 4, and R SiCl , in which R is a n 4-n hydrogen atom, an alkyl group having Cl - 10, alkoxy, haloalkyl, aryl group, or halosilyl group having Cl - 8 or halosilylalkyl group; and n is an integer of 0 - 3.
[4] 4. The process for polymerizing or copolymerizing ethylene according to claim
3, wherein the titanium compound is at least one selected from the group
consisting Of TiCl4, TiBr4, TiI4, Ti(OCH3)Cl3, Ti(OC2H5)Cl3, Ti(OC2H5)Br3, Ti(O(i-C H ))Br , Ti(OCH ) Cl , Ti(OC H ) Cl , Ti(O(i-C H )) Cl , Ti(OC H )
4 9 3 3 2 2 2 5 2 2 4 9 2 2 2 5 2
Br , Ti(OCH ) , Ti(OC H ) and Ti(OC H ) .
2 3 4 2 5 4 4 9 4
[5] 5. The process for polymerizing or copolymerizing ethylene according to claim
1, wherein the halogenated saturated hydrocarbon compound is at least one selected from the group consisting of ethyldichloride, chloroform, ter - butyl chloride, tetrachloromethane, ethylbromide, tert - butyliodide, n - butylbromide, n - butyliodide and n - butylfluoride.
[6] 6. The process for polymerizing or copolymerizing ethylene according to claim
1, wherein the washing process using a halogenated saturated hydrocarbon compound in the step (iv) is repeated once to 5 times.
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RU2567391C2 (en) | 2009-08-21 | 2015-11-10 | Чайна Петролеум Энд Кемикал Корпорейшн | Catalyst component for ethylene polymerisation, preparation thereof and catalyst including catalyst component |
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- 2006-01-12 KR KR1020060003449A patent/KR100715265B1/en not_active IP Right Cessation
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- 2006-12-28 EP EP06835548.6A patent/EP1971620B1/en not_active Expired - Fee Related
- 2006-12-28 JP JP2008550214A patent/JP4898835B2/en not_active Expired - Fee Related
- 2006-12-28 CN CN2006800509265A patent/CN101374868B/en not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
---|---|
US20090221771A1 (en) | 2009-09-03 |
EP1971620A4 (en) | 2012-06-06 |
EP1971620B1 (en) | 2015-06-17 |
JP4898835B2 (en) | 2012-03-21 |
JP2009523187A (en) | 2009-06-18 |
US7754833B2 (en) | 2010-07-13 |
EP1971620A1 (en) | 2008-09-24 |
CN101374868A (en) | 2009-02-25 |
CN101374868B (en) | 2010-09-15 |
KR100715265B1 (en) | 2007-05-04 |
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